Mordant disazo dyestuffs



Patented Feb. 28, 1928.

UNITED STATES.

1,660,625 PATENT OFFICE.

WIIBRLK NEELIEIEB, 01" LEYEBKUBEN-ON-THE-RHINI, LED WERNER BEBNEB, OFLEIPZIG, GEBIIZANY, ASSIGHOBS 'I'O GBABSELLI 'DYESTUFF CORPORATION, 01*NEW YDBK, R. Y., A CORPORATION 01' DELAWARE.

161mm mam n zssrorrs.

I In Drawing. Appllcfilon filed itrch fl, 1927. Serial Io. G294, and InGermany Inch 24. 1826.

This invention relates to nlordunt disazo dyestuffs of the generalformula:

(meta) H000 C0011 (meta) (pen) HO-R-N=NR|-N=NR 01] (para) (meta) B0138011! (meta) 5 in which R is the residue of a -phenylenediaminecompound, i. e, p-pheny ene diam-inc no (menu) uooo coon (mm mmno-nn=N-a.N=N-u on pm (meta) H 8 (meta) in which R is the residue of ap-phenylenediamine compound, as describe above, and

R is an aryl residue of the benzene series having a free position metato the M0 bridge, and otherwise substituted or not by, of halogen,alkyl, or other substituents as escribed above.

The new dyestuffs possessoonsidcrably improved dyeing properties ascompared with the corresponding unsulfonated compounds, beingparticularly ads ted for cotton printing. rintings thereo obtained withchromium acetate surpass those of all hitherto known dyestuffs of thisseries with res act to their ight-, soa ing-, andchlorineast-' ness procrties. T ey are in their dry pulverized orm orange to brown powderssoluble in concentrated sulfuric acid generally with a violet colorationand in water wi an orange to brown coloration. Upon reduction withstunnous chloride and hydrochloric acid they yield phenylene-diaminecompounds and eompoun 5 having the formula:

Under the conditions obtained in lhc following example the snlfonie ucidgroup onion: the orlho-position to the h ydroxyl group of the salicylicacid residue. If the orthoposition wcr'. uh-endy occupied, sulfomdinnwould not take place at all.

l;:cn.mple.--The dinzo compound obtained from 257 parts by weight ofp-amino benzene uzo-salicylic acid in the customary manner is introducedat 0 C. into a solution of 160 parts by weight of salicylic ueid and 350parts by weight of sodium carbonate in 1000 parts walcr. parts by weightof 30"" caustic soda solution are slowly added to the homogeneous magmawhile stirring. The coupling is complete after several hours. Thebenzene-1.4-disazo salicylic acid, which is isolated by acidification,is when dry it vcllowish brown powder, insoluble in water.

ts sodium salt is ditiicultly soluble in water giving a yellowish browncoloration. The solution in concentrated sulfuric acid possesses areddish violet coloration.

Forthe sulfonation 10 parts by weight of the disazo dyestuff formed asdescribed above, are introduced into 80 parts by weight of olcum (20 o)with stirring and the mixture is heats for 8 hours at about to C. Thecooled sulfonation mixture is poured into arts of water and theseparated sulfonate dyestufl' is filtered oil. The sulfonatcd dyestufl'is then dissolved in water containin :1. small excess of sodiumcarbonate, salted out and dried. A reddish brown powder soluble in waterwith an orange red coloration and soluble in sulfuric acid with areddish violet coloration is thus obtained. By chromium printing oncotton 0, yellow orange dyeing is obtained, which dyeing is fast tosoaping and to li ht. The dyestufi in the form of its free aci has mostprobably the formula B000 CODE After being dried and ulverized it is areddish-brown owder so uble in concentrated sulfuric aci with a violetcoloration and in water with an oran e-yellow coloration.

Upon reduction Wlfil stannous chloride and hydrochloric acid it yieldslA-phenyl ene-diamine and 4-.amino-2ehydroxy-benzene-3-sn 1fo-l-carboxylic acid.

Instead of the salicylic acid of the foregoing example other .o-hydroaclds of benzene or ,suhst'itutron roducts thereof, such aselderly-compounds, m which one o'rthwposition and the parlvposition tothe hydroxyl group ure nnoecupied such, for example. as m-cresotinicacid and xylenol carboxylic acid be employed and instead of 'pheuylenediamine there can be used its omologmes, derivatives or substitutionproducts. The dyestnfis obtained as a result of these substitutions?show only slight differences in properties from the salicylic aciddisazo dyestufi' of the example.

We claim 1. As new products, mordunt disazo' dyestufls which in the formof their free acids have most probably theformulu:

no.3 on;

In testimony whereof we have hereunto set our hands.

VVILHELM NEELMEIER 'WERNER REBNER.

ene-dinn'iine and 4-amino-2-hydroxy-benzene-3-sulio-l-carboxylic acid.

Instead of the salicylic acid of the foregoing example other o-hydroxcarboxylic acids of benzene or substitution products thereof, such uscliloro-conipounds, in which one orthoposition and the para-position tothe hydroxyl group are unoccupied such, for example. as ln-eresotinicacid and xylenol cnrboxylic arid be employed and instead of p-phenylene(linniine there can be used its homologlncs. derivatives or substitutionproducts. The dreotull's obtained as :1 result 0 these substitutionsshow only slight differences in properties from the salicylic aciddisazo dyestui'f of the example.

We claim i 1. As new products, mordant disazo dye- CERTIFICATE or PatentNo. l, 660, 625.

H O 0 C stuffs which in the form of their free acids in which R is theresidue of a p-phenylenediuuiine compound and R is un nryl residue ofthe benzene series.

2. The disuzo dyestull having in the lfll'lll of its free acid mostprobably the formula:

C()0Ii som In tesiilnon whereof We have hereunto set our hands.

\VILHELM NEELMEIER. WERYER REBNER.

CORRECTION.

Granted February 28, i928, to

WILHELM NEELMEIER ET AL.

It is hereby.

above numbered patent requiring correction as follows: Page certifiedthat error appears in the printed specification of the 2. 1 inc 1, forthe words "4-amino-" read "S-amino-'"; and that the said Letters Patentshould be read with this correction therein that the same may conform tothe record of the case in the Patent Office.

Signed and scaled this 3rd day of April. A. D. 1928.

Sat.

M. J, Moore, 7 Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION.

Patent No. 1,660, 625. Granted February 28, i928, to

WILHELM NEELMEIER ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2.line i, for the words "4-amino-" read "5 amin0-"; and that the saidLetters Patent should be read with this correction therein that the samemay conform to the record of the case in the Patent Office.

Signed and sealed this 3rd day of April, A. D. [928.

M. J. Moore, Sell. Acting Commissioner of Patents.

